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Stereoselective synthesis and properties of new derivatives of (+)-3-carena


Author: Beţ Liudmila
Degree:doctor of chemistry
Speciality: 02.00.03 - Organic chemistry
Year:2011
Scientific adviser: Fliur Macaev
doctor habilitat, professor, Institute of Chemistry, Academy of Sciences of Moldova
Institution: Institute of Chemistry, Academy of Sciences of Moldova
Scientific council: DH 05-02.00.03
Institute of Chemistry, Academy of Sciences of Moldova

Status

The thesis was presented on the 4 October, 2011
Approved by NCAA on the 22 December, 2011

Abstract

Adobe PDF document0.74 Mb / in romanian

Keywords

(+)-3-carene, 4-substituted 2-carenes, electrochemical oxidation, ozonization, chiral ionic liquids, metal complex asymmetric catalysts, organocatalysis. Field of research: organic synthesis

Summary

Dissertation contents: introduction, 4 chapters, general conclusions and recommendations, bibliography - 173 references, 117 pages of the main part, 47 pictures and 18 tables.

Number of publications: results are published in 27 scientific papers.

The aim of the work: the thesis is dedicated to development of stereoselective synthesis of new derivatives of (+)-3-carena, to study of their structure and properties. The research objectives: the objectives of this scientific work include: to investigate selectivity of electrochemical and ozonolytical transformation of 4,7,7- trimethylbicyclo[4.1.0]hept-4-en-3-yl)ethanones; to study chemo - and stereoselectivity of Kondakov’s and Prins’s reaction in functionalized ionic liquids for synthesis multi-purposed 4- substituted 2-carenes; to develop effective schemes of synthesis previously not explored optically active thioureas, optically active ionic liquids, terpenoid-based phosphite-type compounds and their application as promoters in allylic sulfonylation, allylic alkylation, allylic amination, Strecker-type and epoxide ring opening reactions.

Scientific novelty and originality of the research. Stereoselective approach to new derivatives of (+)-3-carene is developed and their properties are studied. For the first time has been realized synthesis of 4-substituted 2-carenes in functionalized ionic liquids. The 4,7,7- trimethylbicyclo[4.1.0]hept-4-en-3-yl)ethanone was explored using a electrochemical and ozonolytical oxidation in synthesis the chiral fragments of natural bioactive product. A new phosphite and phosphoramidite ligands with P*-stereocentres have been prepared with high diastereoselectivety (97-100%). Using these novel ligands, up to 91% ee was achieved in Pdcatalysed asymmetric allylic amination. Rational schemes for the synthesis of novel terpenoidbased ionic liquids and thioureas were proposed. Catalytic syntheses of chiral building blocks, e.g. allyl ethers, cyclopropanes and амines by use terpenoid-based promoters have been realized.

Theoretical and application value of the research. The results of this study will expand knowledge in organic chemistry. The stereoselective transformation of (+)-3-carene was explored using a variety of reactions, e.g. oxidation, substitution, cycloaddition, reduction etc. This methodology was extended to synthesis the key chirones for obtaining practically important organic compounds - pheromones of Diabrotica virgifera and cytotoxic agents Anthoplalone as well as Astrogorgin.